Water-soluble phthalocyanines containing quaternary or ternary salt groups and synthesis thereof



Patented Feb. 20, 1951 WATER-SOLUBLE PHTHALOCYANINES CON- TAININGQUATER-NARY R TERNARY SALT GROUPS AND SYNTHESIS THEREOF Norman HultonHaddock and Clifiord Wood,

Blackley, England, assignors to Imperial Chemical Industries Limited, acorporation of Great 1 Britain No Drawing. Application March 18, 1949,Serial No. 82,295. In Great Britain December 6, 1944 1'7 Claims. (Cl.260-3145) The present invention relates to the manufacture of newWater-soluble phthalooyanine derivatives and, more particularly, relatesto phthalocyanine derivatives which contain quaternary or ternary saltgroups and are green dyestuffs suitable for dyeing textile materials.

This application is acontinuation-in-part of our copending application,Serial No. 632,786, filed December 4, 1945, now U. S. Patent 2,464,806.

According to the present invention, we manufacture the new water-so1ublephthalocyanine derivatives from phthalocyanine compounds which carrypendant aryl nuclei attached-to the phenylenenucleiof the fundamentalphthalocyanine complex through linking atoms or groups of atoms and bearn chloromethyl or bromomethyl groups, wherein n represents a numeralgreater than 1 and at least (-n-l) ofthechloro-or bromomethyl groups arecarried inthependantaryl nuclei, by a process which comprises treatingthe phthalocyanine compound by known methods for replacing the chlorineor bromine atoms thereof lay quaternary or ternary salt groups. Thelinking atoms or groups ofatoms referred toabove for the purposes ofthepresent invention may be a monatomic bridging link, for

The new water-soluble derivatives thus obtained are compoundsof'theformula R(CI'I2X)n, wherein R represents the -molecule of a metalor metal-free phthalocyanine compound carrying pendant aryl nucleiattached to the .phenylene nuclei of the fundamentatphthalocyanine'complexthrough linking atoms or groups of atoms. n is a number greaterthan 1, at least x (11-1) of the CI-I2X radicals are carried inthe.pendant aryl groups, and X is a quaternary or ternarylsalt group.

Suitable phthalocyanine derivatives for: use. in the process of thepresent invention includepior. example, coppertetra-(chloromethyl)-tetra-4- benzoyl-phthalocyanine, coppertetra-(chloromethyl) tetra-- (p-tolylmercapto) -phthalocyanine, andcopper tetra-(chloromethyl) tetrar i- (p-tolylsulphonyl)-phthalocyanine.

The chlorine or bromine atoms of the chloroor bromo-methyl derivativesofphthalocyanine are replaced by quaternary or ternary salt groups as saidby known means. These include, for example:

(1) Heating the chloroor-bromo-methyl derivative with a tertiary amineto convert it to a quaternary ammonium salt. Suitable tertiary aminesfor this purpose include, for example, pyridine,hexahydrodimethylaniline, triethylamine, and diethylaminoethyl' alcohol.

-(2) Causing the chloroor bromo-methyl derivativeto react with an alkalimetal derivative of a mercaptan of the formula RSI-I wh rein R may be asubstituted or unsubstituted. alkyl, cycloalkyl, aralkyl or arylradical, thus replacing the chlorine or bromine atoms by RS- radicals,and

then treating the so-obtained sulphide with such an ester as is known toconvert sulphides into ternary sulphonium salts, for example withdimethylsulphate or methyl p-toluenesulphonate. Suitable mercaptanswhich may be used in this process include, for example, methylmereaptan,n-butyl mercaptan, cyclo-hexyl mercaptan, benzyl mercaptan thiophenoland p-thiocresol.

(3) Causing the chloroor bromo-methyl de- Jrivativeto react with athiourea so as to convert it into an isothiouronium salt. Suitablethioureas which may be used for this purpose in clude thiourea, N-methylthiourea, N-phenylthiourea, N:N-dimethylthiourea,NzN-dimethylthiourea, N:N:N-trimethylthiourea, and tetramethylthiourea.

The new phthalocyanine derivatives of this invention are soluble inWater giving bright green solutions from which cotton or other textilematerial-is dyed in bright green shades of very good fastness to washingtreatments and to light. In

7 some cases, it isadvantageous to assist solution in water, for exampleby the addition of suitable surface tension reducing agents. We havefound that condensation products of ,B-naphthol and ethylene oxide areparticularly suitable for this purpose. It is a further feature of theinvention to use these quaternary and ternary salts as dyestuffs.

The invention is illustrated but not limited by the following examplesin which parts are by weight:

Example 1 10 parts of copper tetra-(chloromethyl) -tetra-4-benzoyl-phtha1ocyanine (made as described below) and parts ofp-ethoxyethanol are milled during 16 hours with .80 parts of coarsegravel in a bottle rotating at about revolutetra- (methylmercaptomethyl)-tetralbenzoylphthalocyanine.

The so obtained copper tetra- (methylmercaptomethyl)-tetra-4-benzoyl-phthalooyanine and 55 parts of dimethyl sulphate areheated together at 99 C. during 15 minutes. The mixture is then cooledand 150 parts or" acetone are added and the suspended blue solid isfiltered off and washed with acetone. The solid residue is dried byexposure and consists of a blue powder which is readily soluble in watergiving a bright greenishblue solution which dyes cotton in brightgreenish-blue shades of excellent fastness to washing and to light.

The copper tetra-(chloromethyl) -tetra-4-benzoyl-phthalocyanine employedabove may be made as follows: To 30 parts of coarsely-powdered anhydrousaluminum chloride 11 parts of anhydrous triethylamine are graduallyadded. The temperature of the mixture, which becomes liquid, risesduring the addition to about 150 C. The mixture is stirred and allowedto cool to 60 C. and then 3.9 parts of sym-dich orodimethyl ether areadded, the temperature being kept below 70 C. The resulting grey mixtureis cooled to 55 C. and stirred while 5 parts of coppertetra-4-benzoyl-phthalocyanine are added to it in portions, thetemperaure being kept between 55 and 60 C. A deep brown liquid is thusobtained. This liquid is heated at 69:2" C. during 60 minutes, and it isthen poured into 300 parts of water. The bright blue suspension soobtained is filtered and the blue solid is washed free from acid withwater and finally washed twice with alcohol. It is then dried at 641 C.A blue powder is obtained which contains 12.2% of chlorine and consistsprincipally of copper tetra-(chlo- V romethyl) -tetra-4-benzoylphthalocyanine.

Example 2 A mixture of 5 parts of copper tetra-(chloromethyl) -tetra i(p tolylrnercapto) phthalocyanine, (which may be made as describedbelow), 12 parts of tetramethylthiourea and 12 parts of water are heatedat 95-100 C. for 10 minutes. The solution so obtained is cooled anddiluted with 50 .parts of acetone, and the precipitated solid isfiltered off, washed with acetone and dried by exposure to the air. Theproduct is a dark green powder which dissolves in water giving ayellowish-green solution. This solution dyes cotton in yellowish-greenshades. The copper tetra-(chloromethyl)-tetra-4-(ptolylmercapto)phthalocy anine employed above is made as follows: To. 30 parts ofcoarsely-powdered anhydrous aluminum chloride 7.5 parts of coal-tarpyridine of boiling range 115-140 C. are gradually added. lhetemperature of the mixture, which becomes liquid, rises during theaddition to about 150 C. The mixture is stirred and allowed to cool to60 C. and then 6.5 parts of sym-diohlorodimethyl ether are added, thetemperautre being kept below 79 C. The resulting yellow melt is cooledto 40 C. and stirred while 5 parts of coppertetra--(p-tolylmercaptoiphthalocyanine (which may be made by heatingtetra--chlorophthalocyanine with p-thio- I cresol in benzyl'alcohol) areadded to it in portions, the temperature being kept between ill" and 50C. The liquid is heated at 50 C. for 30 minutes and it is then pouredinto 300 parts of water. The green suspension so obtained is filteredand the green solid is washed free from acid with water and finallywashed twice with alcohol. It is then dried at 60 C. and 5.85 parts of agreen powder are obtained, consisting prinoipally of coppertetra-(chloromethyl)tetra- (p-tolylmercapto) phthalocyanine.

Example 3 In place of the 5 parts of copper tetra-(chloromethyl) -tetra(p-tolylmercapto) phtl1alocyanine employed in Exampie 2 there are used 5parts of the chloromethylated product from the interaction of copperhexadecachlorophthalocyanine with phenol described below. The prod;

uct dissolves in water, giving a green solution which dyes cotton ingreen shades.

The chloromethylated product from the interaction of copperhexadecachloro-phthalocyanine with phenol employed above is made asfollows:

A mixture of 21 parts of copper hexadecachloro-phthalocyanine and asolution of 1'52 parts of sodium in 280 parts of phenol is heated in aclosed vessel at 225-230 C. for 3 hours. The mixture is acidified withhydrochloric acid, and the phenol removed by steam distillation. Thegreen suspension so obtained is filtered and the green solid is washedfree from acid with water and finally washed twice with alcohol. It isthen dried at 190 C. and 21 parts of a green powder are obtained, whichcontains 2.6% of chlorine. The product obtained is a mixture of copperphthalocyanine derivatives containing chloro, hydroxy and phenoxysubstituents attached to the phenylene nuclei of the fundamentalphthalocyanine complex but containing no hydrogen atoms attacheddirectly to the phenylene nuclei of the fundamental phthalocyaninecomplex. 5 parts of the product are dissolved in parts of methylhydrogen sulphate and 10 parts of sym-dichlorodimethyl other are added.The mixture is heated at 60 C. for 30 minutes and it is then poured into200 parts of water. The green suspension so obtained is filtered and thegreen solid is washed free from acid with water and finally washed twicewith alcohol. It is then dried at 60 C. and 5.65 parts of a green powderare obtained. The product contains :2 15.5% of side chain chlorinesituated in the substituent chloromethyl groups.

Example 4 romethyl) tetra-4-(p-tolylmercapto) -phthalocyanine employedin Example 2 there are used 5 parts of copper tetra-(chloromethyl)-tetra-4- (p-tolylsulphonyl) -phthalocyanine (made as described below).The product is a dark blue powder which dissolves in water giving agreenishblue solution which dyes cotton in greenish-blue Water and 4parts of ammonium persulpnate are added. '15 parts of concentratedsulphuric acid are added gradually with good stirring, keeping thetemperature at 2025 C. The mixture is stirred at 20-25 C. for a further30 minutes and it is then added to 200 parts of water. The

blue suspension so obtained is filtered and washed free of acid withwater. It is dried at C. and 3.2 parts of a blue powder are obtained.This consists principally of copper tetral-(p-tolylsulphonyl)phthalocyanine.

To 3.) parts of coarsely-powdered aluminum chloride 7.5 parts ofpyridine are added. The

temperature of the mixture, which becomes liquid, rises during theaddition to about 150 C. The mixture is stirred and allowed to cool to60 C. and then 2.6 parts of sym-dichlorodimethyl ether are added, thetemperature being kept below 70 C. The resulting grey mixture i cooledto 5.0 C. and stirredwhile 2 parts of coppertetra-4-(ptolylsulphonyl)-phthalocyanine are added to it in portions,the temperature being kept between 50 C. and 60 C. The mixture is heatedat 60 C. for 15 minutes and it is then poured into 300 parts of water.The blue suspension so obtained is filtered and the blue solid is washedfree from acid with water and finally washed twice with alcohol. It isthen dried at 60 C., and 2.3 parts of a blue powder are obtained. Itconsists principally of copper tetra-(c'hloromethyl)-tetra-4-(-p-toly1sulphonyl) -phthalocyanine.

Emample 5 i parts of copper tetra-(chloromethyl) -tetra-4-(p-to1ylmercapto)-phthalocyanine and 100 parts of pyridine are boiledwith stirring for 10 minutes. The suspension so obtained is cooled anddiluted with 400 parts of acetone and the green solid is filtered off,washed with acetone and dried. The product is soluble in water and thesolution dyes cotton in yellowish-green shades.

The structure of the novel compounds obtained according to thisinvention is typified by that of the product obtained in Example 2above:

wherein X is the tetramethyl-isothiouronium chloride radical graphicallyrepresented as follows:

That portion of the molecule within the square brackets is thefundamental phthalocyanine complex referred to above and in the claimsbelow. The benzene rings of the same are described as the fundamentalphenylene nuclei or as the phenylene nuclei of the fundamentalphthalocyanine complex in order to distinguish the same from the pendantphenyl groups.

In the other examples given above, the -S- linkage may be replaced by-CO-, --SO2 or O, while the methylene isothiouronium salt radical isreplaced by a methylene quaternary ammonium salt radical typified by Oil(the methylene pyridinium chloride radical) or The onium salt radicalmentioned in the claims is to be understood as embracing the saltradical attached to the CH2 group.

It is also to be understood that the expression quaternary ammonium whenreferring to a compound or radical in the claims below is a genericphrase which includes non-cyclic ammonium salts as well as pyridiniumand similar heterocyclic nitrogenous base compounds.

Having thus described our invention, what we claim as new is:

l. A phthalocya'nin'e compound selected from the group consisting ofmetal-phtiialocyanines and metal free phthalocyanines :arr-y pendantaryl nuclei attached to the phenylene nuclei of the fundamentalphthaiocyanine com plex through a monatcznic bridging link, andcharacterized by bearing 1; radicals of the type CI-I2X, wherein 1Lrepresents a numeral. greater than 1, at least (n-l) of said radicalscarried in said pendant aryl ei and represents an onium salt radical sted from the group consisting of the sulfoniurn, iscthiouronium andquaternary ammonium salts of vater soluble acids.

2. A water soluble metal phthalocyanine compound carrying pendant arylnuclei attached to the phenylene nuclei of the fundamentalphthalocyanine complex through a monatomic bridging link, andcharacterized by bearing 12 radicals or" the type --CH2X, wherein nrepresents a numeral greater than 1, at least (11-1) of said radicalsbeing carried in said pendant aryl nuclei and X CHzX GHZX

represents an onium salt radical selected from the group consisting ofthe sulfonium, isothiouronium and quaternary ammonium salts ofwater-soluble acids.

3. A phthalocyanine compound as claimed in claim 1 wherein saidmonatomic bridging link is 4. A phthalocyanine compound as claimed inclaim 1 wherein said monatomic bridging link is --S-.

5. A phthalocyanine compound as claimed in claim 1 wherein saidmonatomic bridging link is -O-.

6. A phthalocyanine compound as claimed in claim 1 wherein saidmonatomic bridging link is '7. A copper phthalocyanine compound carryingpendant aryl nuclei attached to the phenylene nuclei of the fundamentalphthalocyanine complex through a monatomic bridging link, andcharacterized by bearing n radicals of the type CII2X, wherein nrepresents a numeral greater than 1, at least (11-1) of said radicalsbeing carried in said pendant aryl nuclei and X represents an onium saltradical selected from the group 7 consisting of the sulfonium,isothiouronium and quaternary ammonium salts of water-soluble acids.

8. A copper phthalocyanine compound carrying pendant aryl nucleiattached to the phenylene nuclei of the fundamental phthalocyaninecomplex through a mcnatomic bridging link, and characterized by bearing11. methylene-ternarysulfonium salt radicals, wherein n represents anumeral greater than 1, at least (11-1) of said radicals being carriedin said pendant aryl nuclei.

9. A copper phthalocyanine compound carrying pendant aryl nucleiattached to the phenylene nuclei of the fundamental phthalocyaninecomplex through a monatomic bridging link, and characterized by bearingn methylene-isothiouronium halide radicals, wherein n represents anumeral greater than 1, at least (n-1) of said radicals being carried insaid pendant aryl nuclei.

10. A copper phthalocyanine compound carrying pendant aryl nucleiattached to the phenylene nuclei of the fundamental phthalocyaninecomplex through a monatomic bridging link, and characterized by bearing11 methylene-quaternary ammonium halide radicals, wherein n represents anumeral greater than 1, at least (n-l) of said radicals being carried insaid pendant aryl nuclei.

11. A copper phthalocyanine compound carrying pendant aryl nucleiattached to the phenylene lected from the'group consisting of .CHzCl andCHzBr, wherein n represents a numeral greater than 1, and at least(11-1) of said radicals are carried in said pendant aryl nuclei, thestep which comprises replacing the halide atoms of said phthalocyaninecompound with an onium 15. A process as claimed in claim 13 wherein saidphthalocyanine compound is reacted with a thiourea to replace thehalideradicals with isothiouronium salt radicals.

16. A process as claimed in claim 13 wherein said phthalocyaninecompound is reacted with an alkali-metal salt of a mercaptan selectedfrom the group consisting of alkyl, aralkyl and aryl mercaptans, andthen subjecting the intermediate thus obtained to reaction with a methylester,

whereby to convert the mercaptide radical into REFERENCES CITED Thefollowing references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,479,491 Haddock Aug. 16, 1949

1. A PHTHALOCYANINE COMPOUND SELECTED FROM THE GROUP CONSISTING OFMETAL-PHTHALOCYANINES AND METAL-FREE PHTHALOCYANINES WHICH CARRY PENDANTARYL NUCLEI ATTACHED TO THE PHENYLENE NUCLEI OF THE FUNDAMENTALPHTHALOCYANINE COMPLEX THROUGH A MONATOMIC BRIDGING LINK, ANDCHARACTERIZED BY BEARING N RADICALS OF THE TYPE -CH2X, WHEREIN NREPRESENTS A NUMERAL GREATER THAN 1, AT LEAST (N-1) OF SAID RADICALSBEING CARRIED IN SAID PENDANT ARYL NUCLEI AND X REPRESENTS AN ONIUM SALTRADICAL SELECTED FROM THE GROUP CONSISTING OF THE SULFONIUM,ISOTHIOURONIUM AND QUATERNARY AMMONIUM SALTS OF WATER-SOLUBLE ACIDS.